Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

为什么要引入溶剂的渗透因子

阐明了引入溶剂渗透因子的必要性,较详细地介绍了两种渗透因子及它们间的关系。     

含气率对PTS时压力容器内流动与传热的影响

本文对反应堆压力容器紧急安注时的流动与传热特性在1/10的模型上进行了流动可视化、局部传热系数以及混合函数的试验研究。针对三个热冲击敏感区域的部分测点,比较了环腔流速为0.5m/s、安注流速为1～30 m/s时不同含气率对下降环腔内流动与传热特性的影响,得出并分析了不同测点传热系数、混合函数的变化规律。研究结果表明:随着含气率增大,安注流体与环腔流体的混合增强;下降环腔内的含气率对小安注流速时的流动与传热影响显著,而对大安注流速时影响较小。     

压力淬火过程中锗的相结构研究

 应用高压原位差热方法，直接测量了压力下锗的固化参数─—固化温度与过冷度。高压差热信号表明，当压力大于3 GPa时，锗在凝固过程中可能发生结构相变。X射线结构分析表明，在最终的样品中除GeⅠ相外，还形成GeⅢ相和GeⅣ相。     

二氧化钒薄膜的低温制备及其性能研究

针对VO₂薄膜在微测辐射热计上的应用，采用射频反应溅射法，在室温下制备氧化钒薄膜；研究了氧分压对薄膜沉积速率、电学性质及成分的影响.通过调节氧分压，先获得成分接近VO₂的非晶化薄膜，再在400℃空气中氧化退火，便可制得高电阻温度系数，低电阻率的VO₂薄膜，电阻温度系数约为-4%/℃，薄膜方块电阻为R_□为100—300kΩ；薄膜在室温下沉积，400℃下退火的制备方法与微机电加工(micro electromechanic 关键词： 二氧化钒 电阻温度系数 氧分压 射频反应溅射法     

烟气中Hg的氧化机理的研究

本文对Ｈｇ与Ｃｌ２在烟气中的氧化反应进行了热力平衡计算和动力学计算。平衡计算的结果表明有ＣＩ元索存在时Ｈｇ的氧化率为１００％，而在相同的条件下动力学计算纺果为Ｈｇ的氧化率在２０％～８０％之间变化，与实验结果吻合。实际的氧化反应是一种超平衡状态，不能达到理想的平衡状态。因此应采用动力学与热力平衡分析相结合的方法研究Ｈｇ在烟气中的反应机理。同时，计算结果显示Ｃｌ含量对Ｈｇ的氧化率的影响很大．     

Roles of SiH4 and SiF4 in growth and structural changes of poly-Si films

The structural properties of polycrystalline silicon films, prepared by plasma enhanced chemical vapor deposition system, with different flow rates of SiH₄/SiF₄ mixtures at 300 °C were investigated. This study indicates that the low hydrogen coverage on the growing surface, under optimum fluorine radicals, will be leaded to an improvement of crystallized area as compared with case of high hydrogen coverage surface. Moreover, the studies of the role of SiH₄ and SiF₄ radicals show that the SiH₄ radicals are important in the nucleation and growth of grains. However, SiF₄ radicals are effective in the structural change of grain boundaries regions and by this way, in the present system, establish the growth of grains under the dominant 〈1 1 0〉 direction. The stress investigation indicates that addition of high flow rate of SiF₄ in amorphous film, results in the nearly stress free films. Finally, we found that the changes in g-value reflect the changes in the intrinsic compressive and tensile stress in the both polycrystalline and amorphous silicon films.     

超临界流体触媒作用下石墨-金刚石转变

 研究了超临界流体CO₂在石墨-金刚石转变中的触媒作用。实验中，采用Ag₂O作为流体触媒的先驱材料，在7.7 GPa压力下，Ag₂O在1 200 ℃分解成Ag和O₂，O₂与石墨套管在高温高压下反应形成CO₂超临界流体。研究结果表明，在7.7 GPa和1 500 ℃以上温度条件下，石墨在CO₂流体触媒的作用下可转变为金刚石晶体，在1 500～1 700 ℃温度范围内合成出的金刚石具有完好的八面体形貌，与天然金刚石的生长特征非常相似。     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Convergent Flows of Molten Polymers Modeled by Generalized Second-Grade Fluids of Power-Law Type

The molding processes of polymer melts involve geometrically complex dies. Such dies are usually tapered or streamlined to achieve a maximum output rate under conditions of laminar flow. The model of a generalized second-grade fluid of power-law type is used and the results obtained are illustrated by examples of convergent flows in conical and wedge-shaped dies.